Antitack agent



Aug. 9, 1949. H. M. SINGLETON ANTITACK AGENT Filed Jan. 2, 1947 wEroa 8.52m einem ATTORNEY.

Patented Aug. 9, 1949 UNITED ST ANTITACK AGENT tion of Delaware Application January 2, 1947, Serial No. 719,728

i Claim. 1

The present invention is directed to a method for handling high molecular weight polymers as a dispersion in an aqueous solution. More particularly, the invention is concerned with a method for dispersing butyl rubber in an aqueous solution in such a manner that formation of agglomerated bodies is substantially eliminated.

In the production of the hydrocarbon polymer known to the art as butyl rubber, it is conventional practice to polymerize a mixture of a mono-olefin, such as isobutylene, and a diolefln, such as isoprene, in a diluent at a loW temperature of the order of 40 to 175 F. employing a Friedel-Crafts type catalyst, such as aluminum chloride, to obtain a polymer of high molecular Weight and having vulcanizable characteristics. The polymerization is conducted at low temperatures preferably in the range of about 100 to 140 F. with the hydrocarbon diluted with a diluent such as an alkyl halide; methyl chloride has been used successfully commercially. The Friedel-Crafts catalyst, aluminum chloride for example, is also dissolved in a solvent which may be methyl chloride and the solution is chilled to the aforesaid low temperature range before contacting the diluted hydrocarbon feed.

It is customary to employ a feed comprising approximately hydrocarbon and 75% alkyl halide. The hydrocarbon component of the feed stock may include ST1/2% isobutylene and the remaining 21/2% isoprene. Variations in the hydrocarbon feed component of the feed stock and the diluent may be employed successfully.

After the polymer has been formed as a slurry of rubber particles in the diluent, the polymer must be separated and then further processed before it can be successfully employed in the manufacture of rubber goods. In order to handle this rubber dispersion in the diluent, it is neces'- sary to remove this rubber from the diluent and the unreacted feed stock. This is usually done by flash distillation in which the hydrocarbon and the diluent are vaporized from the rubber particles and is usually accomplished by dumping the slurry suspended in the diluent and unreacted hydrocarbon into an aqueous media such as alcoholic solutions or Warm water. The latter at a temperature of about 140 to 170 F. is usually employed commercially. However, this latter operation is attended by difficulties since the ne rubber particles have a tendency to adhere together, agglomerate, and coalesce into large rubbery bodies which cannot be handled in pipelines and pumping equipment without clogging the equipment. It is, therefore, necessary in the commercial operation of the process to add dispersion or anti-tack agents to prevent formation of the agglomerated bodies and to maintain the rubber particles in a finely divided condition. The metallic salts of fatty acids, which are relatively insoluble in water and only slightly soluble in the rubber polymer, have been employed successfully. There is one great objection to ernpolyment of the metallic salts of the fatty acids as the dispersion or anti-tack agent since these materials in their course of manufacture are dried and reground to particle size specification prior to shipment to points of utilization. It is postulated that during the drying operation a certain amount of the metallic soap is fused together in the form of lumps and, therefore, requires regrinding. It has been demonstrated that portions of the fused and reground material is ineffective as a dispersion and anti-tack agent, and, hence, a serious economic loss is suffered.

It is, therefore, the main object of the present invention to provide a method of forming an antitack and dispersion agent for high molecular Weight hydrocarbons, in situ, in which a material having the desirable properties is obtained in finely divided form.

In accordance with the present invention, a saturated aqueous solution of an alkali metal salt of a substantially saturated aliphatic fatty acid is formed. The solution is then agitated violently with a salt of an alkaline metal selected from groups Il and III of the periodic table while controlling the pH of the admixture between about 8 and 8.5 and maintaining the temperature below 150 E'. The pH of the admixture is controlled by adding an aqueous solution of sodium hydroxide to the admixture during the agitation. After the admixture is formed, it is then added to the reaction product of a tertiary mono-olefin and a diolefin which has been formed in the presence of a Friedel-Crafts type catalyst at a temperature in the range from about to 140 F.

In proceeding in accordance with the present invention, an alkali metal salt of a saturated aliphatic fatty acid is first dissolved in Water to produce a lvery viscous solution thereof. The salt of the metal selected from groups II and III of the periodic table is then added to the viscous solution either as a concentrated aqueous solution or as a solid. This latter materialgoes into solution without formation of lumps. If, on the other hand, the alkali metal salt of a saturated aliphatic fatty acid were added to the solution of the salt of the metal of groups II or III of the periodic table, lump formation would have been Y `barges..material .from 'thev ilash. tank 29.

the operation, it is also important to add a wetting; 102A agent such as sodium sulfonates. Sodium sulonates may be obtained by caustic neutralization of the oil-soluble sulfonic acidsformedduringsulf/ furie acid treatment of solvent extracts.V The amount of the wetting agent, suchas'sodiumsulf I5..

ionates,V is critical in that if an insufficient quantity is employed, reaction product separatesfrom. the solution as a powder whereas if an excess of sodium sulfonates is employed, the reactioniprod uct is wetted to the extent that it does not have 20 suitable anti-tack. andfdispersion properties .when addedfto the; hydrocarbon-polymer. During; this latter. operation, itistalsowdesrable'to add to ythe dispersion agentf a stabilizer.. which during'. the course-.of the-rubber milling andhandling opera tions-will preventthe :rubber from depolymerizingg. fr. stabilizer suchA as phenyl -betanaphthylamine may be used.A

The l present. invention 'will be` further described in' conjunction. withY the;- drawingjin which the single-iigureisin thefformofiaiflow diagram illus.- tratingv one-modiicationthereof.

Referring nowto-thefdrawing, numerals II and i 2 :designate 2 mixing tanks provided with. mixing means" l3- and.. i4 actuated :by prime movers I5 and If-lthrougheshaftsz I1 and. I8. Mixing. tanks Hand; i2 connect byway-offzlines I9 and=20 to manifold?! I.. Lines Ill-rand. 2 0 are. controlled-by valves` 22' and .23 Line'Z-I is-.providedL with a pump 2t' and is yconnected iby.line25 and. branch line- 25.' into:manifold- 2.1'.v Manifold .21j isnconnettedV by line: 2S'rwith-.flash-tankl 29.

InV the` operation of... the invention; sodium stearate. for exa-mple,-.is dissolved-.ineither tank il or i2 in a suitable-amount:offwatento. produce a very viscous solution thereof... Zincnsulfate; is added to the tankeither asa solution or in the solid form while violently agitating the contents of thetanks with' mixing means I3.-and. I4. In tliefdrawing, mixingV tank Il is shown provided with an. inlet linee for the additionzof sodium ,stearate` and zinc sulfate thereto and mixing tank l 2,-is shown'with an inlet line- I0. for thesaddition of sodiumsteara-teand zinc sulfate thereto.- It will. be understood; that the inlet lines-fil andvr- I are shown vfor. illustrative purposes only; as herevtofore explained, the sodium stearate may be .dded in solid-.formandthe zinc. sulfate maybe added either inthe form of asolution or inthe solid form to. theseA mixing tanks. A sucient amount of sodium.. sulfonates, phenyl beta naphthylamine.. and sodium hydroxide. is then added during the course of operation. YAftervthe admixture has been suiliciently agitated to form a.- reac'tion productbetweenthe sodium, stearate and .thezinc sulfate, onefof thetanks, for example tank. l2, may be putinto theoperating system by opening valve..23 inline. andfstartingpump 2li whichpumps the solution through line v26,` manifold 2i. and. lineZinto line. 30. which dis.-v

Mate-Y rial withdrawn from the bottom of iiashtank 29 is largely water. containing the Ydispersion agent. Thismaterial is pumped-bypump 3.I- into delivery pipe 32. intov vwhichacoldstream. of..r.ubber. rpol-ymer dissolved in methyl chloride, for example, is delivered by -way of line 33. The temperature of the solution in line 30 is between 140 and 170 F. while the temperature of the polymer slurry in line B is between -100 and 140 F. it will be readily apparent that the large temperature differential betweenthe two streams entering tank '29.tl`11'o11gli-'rline 3f2..resultsinheating. of the colder of the two streams and distillation of the unreacted hydrocarbons and diluent therefrom. These materials flash from the solution and are discharged from flash tank 29 through line 32 to arecovery stream, not shown. Steam maybe injected by way Online to maintain the temperatureof the aqueous solution in the bottom of tank '29: between 140 and 170 F. At an intermediate-,point from the bottom of tank 29 an aqueous dispersion of rubber particles in water is withdrawn by line 36 and pump 31 to handling and milling facilities, not shown.

While adding` thereaction product of. sodium stearate. and-zinc :sulfate to the.` reaction product otthe. tertiary mono-oleiin and diolen, itmay be desirable: to recirculate.a.part ofthe aqueous solution. thereof back. to. the mixing tank I2. Suitable valves and:v connectionsy are, therefore; provided iii-manifold2-.'I.=v By-pass line 381con.- trolled.. by--valve Bazallowsi recirculation of thereaction .productback into .tank I2.l ValvesV 40,k 4l; and lig-inmanifold. 2Jare provided for control of the. quantities-V of.- solution; flowing from mixing tank I2 to.lash.tank.r29;

When: the contents of tank I2 becomede.- pleted, by asimple manipulation of valve123.: it maybewithdrawn from .operation and by opening valve 22 in.line.. I9.,l tank. II may be placed in operation whilethe-:contentsof tank I2, arebeing renewed by make.. 11p-.0f fresh; solution.` When tank; I I. is. inf-.operationandta-nkI-2 has.`v been taken. off; the.. operating stream,..valve 40 will be closed and.valve.43 in-line..44-op.ened;` Similar tothe flowwith -resizieet to tank. l2., aportionof thereactant. mixture flowing through manifold 2J. maybe returned .totank. I I by. opening valve in .linelwhich al1o.ws...r eturn.ofthe mixture by line 2|, pumpldeline 2'5.,..line; 261,- and'line 46 to. tank I.-I

The aqueous slurry ofhydrocarbon polymer passingl through. liney 3&5.l is.. suitablyY dispersed therein .and the rubber polymers aree coated .with

.an.anti-tack agent-to preventits forming agglomerates land stickingtothe hot parts of the driers, extruders. andmills. with which. it comes into.. contact.. during :itsV .processing operation.

Asuan example. .of .thefoperationY ofthe present invention, a,commercial.run-.in.a butyl rubber plant. was. made..inwhich.the. anti-.tack and .dispersion. agent. inaccordance. with the. present inventioniwas. prepared.. In this particular nun 651pounds.ofyzinesulfate.crystals (ZnSO4.,7H2O.)., lzpoundssodium stearate, Yifxlpcunds of .phenyl beta naphthylamine.1 11.4: quarts` of; sodium sulfonates, 1. quart of%. sodium hydroxidesolu tion. werexmade fup.Y to. a.. total .volume of..500galf lons.inequipment,similar to. tanksv I l. and. I2.. This. solution.hada..total. solids-content` of ap prnximately 0.35 pound. per. gallornv The. sodium stearate. was first.. dissolved. in 200.. gallons of water. The sodium.- hydroxide wasthen added followedf byaddition; of. thesolid zinc. sulfate. A fterthezinc sulfate has completely vreactedwith thesodiumstearateto. .form Zinc. stearate, a.mix-. ture. of phenyl-l beta naphthylaminev and sodium su-.lfonat'es..in 5.. gallons of... water. was. then added and the...total..volumeadjusted.up-*to the. afore;

mentioned 500 gallons. The function od the caustic soda was to control the pH of the mixture. The amount of caustic added gave a pH of 8. Control of alkalinity between 8 and 8.5 gives formation of the desired particle size disperson and anti-tack agent. The temperature employed was below 150 F.

In forming the solution in accordance with the present invention, it is necessary that essentially -a saturated solution of the major components formed andthe material discharged through line 36 was thoroughly dispersed in the water solution and was easily handled in the driers, extruders, and mills making up the nishing processing equipment.

During the course of a comparison between the reaction products of the present invention with zinc stearate produced in conventional operations in which it was dried and reground, it was found that the amount of additive necessary in satisfactorily conditioning the polymer for subsequent handling and milling was reduced by approximately 55% which represents a considerable economic gain.

While the invention has been described with respect to the employment of sodium stearate in forming the zinc stearate in situ, it will be apparent to the skilled worker that stearic acid may comprise one of the starting materials. If desired, stearic acid may be reacted with caustic soda to form sodium stearate and the sodium stearate then formed employed in producing the anti-tack and dispersion agent in accordance with the present invention. Actually in commercial operations, it may be preferred to begin with stearic acid rather than sodium stearate.

Throughout the specification and claim emphasis has been placed on the employment of a metal salt of a saturated aliphatic fatty acid. It is within the spirit and scope of the present invention to employ, as the fatty acid component, a iatty acid which may contain residual unsaturation. When the fatty acid contains residual unsaturation, it is desirable that the amount of unsaturation should not exceed the equivalent to that of stearic acid having an iodine value of 15; best results, however, are obtained with a fatty acid having a residual iodine number of 8 maximum.

The invention has been described and illustrated with respect to the employment of zinc as illustrative of the groups II and III metals. It is contemplated that other metal salts may be used in forming the anti-tack and dispersion agent of the present invention. For example, calcium, magnesium, aluminum, and barium salts may be used effectively. Under some conditions, it may be desirable to use 'salts of these metals in preferance to zinc by virtue of their higher melting points.

The nature and objects of the present invention having been fully described and illustrated, what I wish to claim as new and useful and to secure by Letters Patent is:

A process for preparing an anti-tack agent for a rubbery polymer which comprises the steps of dissolving sodium stearate in water to form a saturated solution, adding zinc sulfate thereto and agitating the mixture violently at a temperature below approximately F., and controlling the pH of the mixture between 8 and 8.5 by adding to the mixture sodium hydroxide and sodium sulfonate solution to form a. solution having a solids content of approximately 0.35 pound per gallon.

HENRY M. SINGLETON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,378,693 Fryling June 19, 1945 2,417,071 Gebhart et al Mar. 11, 1947 

